KR20150009482A - Aromatic polyacetals and articles comprising them - Google Patents

Abstract

The present invention relates to a polymer comprising repeat units having an undermentioned structure. In the formula, R^1, R^2, Ar^1, Ar^2, and Ar^3 are as defined in the present specification. The polymer can be prepared by Suzuki polycondensation. The acetal and/or ketal functionality in the polymer backbone make the backbone-cleavable in acid. The polymer is useful in applications including lithographic photoresists.

Description

[0001] AROMATIC POLYACETALS AND ARTICLES COMPRISING THEM [0002]

The present invention relates to polymers, especially aromatic polyacetals and polyketals.

Chemically amplified photoresists based on poly (methacrylate) and poly (hydroxystyrene) have reached performance limits defined by the trade-off triangle of resolution, line edge roughness and sensitivity. This is the so-called RLS trade-off. There is empirical evidence that attempts to increase one of the important properties using formulation studies are detrimental to the rest of the properties of the triangle. These effects include extreme ultraviolet (EUV) and electron beams, limiting the size of features achievable in high resolution photolithography. One method of escaping the RLS trade-off triangle of chemically amplified photoresists of poly (methacrylate) and poly (hydroxystyrene) systems is to improve the photon absorption, the improved quantum efficiency and the improvement of the catalytic chain reaction Lt; RTI ID = 0.0 > photoresist < / RTI > Additional methods of escaping RLS trade-off triangles of chemically amplified photoresists, such as poly (methacrylate) and poly (hydroxystyrene) chemically amplified photoresists, have been found to result in inconsistent diffusion behavior during photolithography (Kozawa, T, Tagawa, S., Santillan, JJ, Itani, T., Journal of Photopolymer < RTI ID = 0.0 > Science and Technology, 2008, volume 21, pages 421-427). This behavior can be achieved with the aid of skeleton-degradable polymers.

One embodiment is a polymer comprising a plurality of repeating units having the structure:

또는

or

In the above formula

R ¹ and R ² in each occurrence are independently hydrogen, unsubstituted or substituted C _1-18 linear or branched alkyl, unsubstituted or substituted C _3-18 cycloalkyl, unsubstituted or substituted C _6-18 aryl , Or unsubstituted or substituted C _3-18 heteroaryl; R ¹ and R ² are optionally covalently linked to ^{one another} to form a ring comprising -R ¹ -CR ² -, wherein the central carbon is acetal carbon; In each case Ar ¹ , Ar ² , and Ar ³ independently represent an unsubstituted or substituted C _6-18 arylene, or an unsubstituted or substituted C _3-18 heteroarylene; With the proviso that at least one of Ar ¹ , Ar ² and Ar ³ is substituted by at least one functional group selected from hydroxyl, acetal, ketal, ester and lactone.

Another embodiment is an article comprising a polymer.

These and other embodiments are specifically described below.

The inventors have prepared polymers containing unstable acetal groups within the polymer backbone, and optionally additional labile functional groups as pendant for the polymer. Under acidic conditions, depolymerization and deprotection of any acid-sensitive protecting group is achieved at the same time. Thus, the polymer provides improved efficiency of the catalytic chain reaction to poly (methacrylate) and poly (hydroxystyrene). At the same time, polymers may exhibit other properties that make them particularly useful in lithography. These properties include, but are not limited to, high glass transition temperature, high exchange parameters, Ohnishi parameters (improved etch resistance), solubility in solvents conventional in photoresist formulations, thermal stability of the polymer backbone, Solubility in a developing solution, and the like.

This application describes polymers. The co-pending US application serial number _ [Attorney Docket No. DOW0009US] describes monomers for making polymers. The co-pending US application serial number _ [Attorney Docket No. DOW0008US] describes a method of making a polymer. And co-pending US application serial number _ [attorney docket number DOW0008US] describes a photoresist composition comprising a polymer.

Unless otherwise stated, the term "acetal ", as used herein for the sake of brevity, should be understood to be collectively referred to as" acetal " And the term "polyacetal" should be understood as collectively "polyacetal" and "polyketal. &Quot; The term "plurality" as used herein means at least three. Also, the term "polymer" will be understood to encompass oligomers containing as few as three repeating units. The desired number of repeating units will depend on the intended use of the polymer. For example, when a polymer is used in a photoresist composition, it may be preferred that the polymer comprises at least 5 repeating units, specifically 5 to 200 repeating units. As used herein, "substituted" refers to at least one substituent such as halogen (i.e., F, Cl, Br, I), hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, sulfide, disulfide, , C _1-18 alkyl, C _1-18 alkoxyl, C _6-18 aryl, C _6-18 aryloxyl, C _7-18 alkylaryl, or C _7-18 alkylaryloxyl. It will be appreciated that any group or structure disclosed in connection with the formulas herein may be so substituted unless otherwise specified or where such substitution has a significant deleterious effect on the desired properties of the resulting structure. Also, "fluorinated" means containing one or more fluorine atoms introduced into the group. For example, when a C _1-18 fluoroalkyl group is indicated, the fluoroalkyl group may be substituted by one or more fluorine atoms, for example, a single fluorine atom, two fluorine atoms such as 1,1-difluoroethyl groups ), three fluorine atoms (such as ethyl 2,2,2-trifluoroethyl), or a fluorine atom at each free valence of carbon (for example, perfluorinated fire extinguisher, for example _{-CF 3, -C 2 F 5 -} , -C ₃ F ₇ or -C ₄ F ₉ ).

One embodiment is a polymer comprising a plurality of repeating units having the structure:

또는

or

In the above formula

R ¹ and R ² in each occurrence are independently hydrogen, unsubstituted or substituted C _1-18 linear or branched alkyl, unsubstituted or substituted C _3-18 cycloalkyl, unsubstituted or substituted C _6-18 aryl , Or unsubstituted or substituted C _3-18 heteroaryl; R ¹ and R ² are optionally covalently linked to ^{one another} to form a ring comprising -R ¹ -CR ² -, wherein the central carbon is acetal carbon; In each case Ar ¹ , Ar ² , and Ar ³ independently represent an unsubstituted or substituted C _6-18 arylene, or an unsubstituted or substituted C _3-18 heteroarylene; With the proviso that at least one of Ar ¹ , Ar ² , and Ar ³ is substituted by at least one functional group selected from hydroxyl, acetal, ketal, ester and lactone.

When the polymer contains a plurality of repeating units having the following structure

The recurring units may be formed by Suzuki polycondensation of one or more bis (aryl) acetal compounds exhibiting the following structure:

In the above formula

B ^x represents a boron-containing functional group bonded to Ar ¹ through a boron atom;

Y represents chloro, bromo, iodo, triflate, mesylate or tosylate;

이고, 여기에서 R³ 및 R⁴는 각각 독립적으로 C_1-18 알킬, C_3-18 사이클로알킬 또는 C_6-18 아릴이며; R³ 및 R⁴는 임의로 상호간에 공유적으로 연결되어 -R³-O-B-O-R⁴- 를 포함하는 환을 형성한다.R ¹ , R ² , Ar ¹ and Ar ² are as defined above. Examples of the group B ^x is a -BF ₃ ^- M ⁺ may be cited, in each case where M ⁺ is independently an alkali metal cation, or unsubstituted or substituted ammonium ion; -B (OH) ₂ ; And

, Wherein R ³ and R ⁴ are each independently C _1-18 alkyl, C _3-18 cycloalkyl or C _6-18 aryl; R ³ and R ⁴ are optionally covalently linked to each other to form a ring containing -R ³ -OBOR ⁴ -.

There are at least two methods of forming a polymer comprising a plurality of repeating units representing the following structure:

The first method involves the reaction of a bis (aryl) acetal compound representing the following structure with a bis (aryl) acetal compound having the structure Y-Ar ³ -Y, wherein Y and Ar ³ are as defined above and Y in each case is defined independently (Leaving group) arylene: < RTI ID = 0.0 >

Wherein B ^x , R ¹ , R ² , Ar ¹ and Ar ² are as defined above and in each case B ^x is independently defined.

The second method comprises reacting a bis (aryl) acetal compound and a structure B ^x -Ar ³ -B ^x , wherein B ^x and Ar ³ are as previously defined and B ^x is independently defined in each case ) ≪ / RTI > of Suzuki polycondensation of bis (leaving group) arylene,

Wherein Y, R ¹ , R ² , Ar ¹ and Ar ² are as defined above, and in each case Y is independently defined.

An overview of Suzuki polycondensation and the resulting polymers is described in Schlueter et al., In Macromolecular Rapid Communications , 2009, volume 30, pages 653-687 and Journal of Polymer Science, Part A, Polymer Chemistry , 2001, volume 39 , pages 1533-1556. The present inventors have found that catalysts that are particularly active in polymerization include those having the following structure:

In the above formula

In each case R ¹⁴ is independently selected from the group consisting of unsubstituted or substituted C _1-18 linear or branched alkyl, unsubstituted or substituted C _3-18 cycloalkyl, unsubstituted or substituted C _6-18 aryl, Substituted peracenyl; R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ independently represent hydrogen, C _1-6 linear or branched alkyl, C _3-6 cycloalkyl, or phenyl; Z is selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano (-CN), cyanate (-OCN), isocyanate (-NCO), thiocyanate (-SCN), isothiocyanate (-NCS) NO ₂ ), nitrite (-ON = O), azide (-N = N ⁺ = N ^- ), and hydroxyl. A method for preparing such a catalyst is described in CCC Johansson Seechurn, SL Parisel, and TJ Calacot, J. Org. Chem. 2011, 76 , 7918-7932, Not).

One advantage of the polymers according to the invention is that the Suzuki polycondensation used in their preparation tolerates the polyacetal synthesis and the non-functional, functional groups in which the acetal-containing backbone is formed in the last step. Specifically, at least one of Ar ¹ , Ar ² and Ar ³ (if present) is substituted by at least one functional group selected from hydroxyl, acetal, ketal, ester and lactone.

The acetal may be a monovalent acetal having the structure:

-OC (H) (R < ⁵ >) -OR < ^{6 &}

Wherein R ⁵ and R ⁶ are independently selected from the group consisting of unsubstituted or substituted C _1-18 linear or branched alkyl, unsubstituted or substituted C _3-18 cycloalkyl, unsubstituted or substituted C _6-18 aryl, &_{Lt; /} RTI > substituted C3- _{C18heteroaryl} ; Optionally, R ⁵ or R ⁶ is covalently linked to the polymer backbone (e.g., R ¹ or R ² , or via attachment of one of the Ar ¹ , Ar ^2, and Ar ³ , ). In these embodiments, the acetal is part of a ring structure. The ring structure may or may not include the following structure:

Ar ¹ -OCO-Ar ² .

In some embodiments, R ⁵ and R ⁶ are covalently linked to each other to form a ring structure. Specific examples of monovalent acetals having the structure -OC (H) (R ⁵ ) -OR ⁶ are as follows:

The acetal may be a divalent cyclic acetal bonded to Ar &^lt; ¹ >, Ar &^lt; ² > or Ar < ³ > through an oxygen atom,

Wherein Ar ⁿ is selected from the group consisting of Ar ¹ , Ar ² or Ar ³ (if present) or a combination of Ar ¹ and Ar ² (eg, one acetal oxygen directly bonded to Ar ¹ and the other directly connected to Ar ² Or a combination of Ar < ² > and Ar < ³ >; R ¹⁰ is an unsubstituted or substituted C _1-18 straight or branched alkyl, unsubstituted or substituted C _3-18 cycloalkyl, unsubstituted or substituted C _6-18 aryl, and unsubstituted or substituted C _{3- 18} heteroaryl. ≪ / RTI > In some embodiments, the cyclic acetal is part of a ring structure comprising the structure:

Ar ^{1 is} -OC (R ¹ ) (R ² ) -O-Ar ² .

In another embodiment, the cyclic acetals are not part of this ring structure.

The ketal can be a monocarboxylate which exhibits the following structure:

^{-OC (R 7) (R 8} ) -OR 9,

Wherein R ⁷ , R ⁸ and R ⁹ are selected from the group consisting of unsubstituted or substituted C _1-18 linear or branched alkyl, unsubstituted or substituted C _3-18 cycloalkyl, unsubstituted or substituted C _6-18 aryl, and And unsubstituted or substituted C _3-18 heteroaryl. Optionally, R ⁷ , R ⁸ or R ⁹ is covalently linked to the polymer backbone such that the acetal is part of a ring structure.

The ketal may also be a cyclic ketal bonded to Ar < ^{1 >} or Ar < ² > through an oxygen atom,

Wherein Ar ⁿ is Ar ¹ or Ar ² , or a combination of Ar ¹ and Ar ² (for example, when one ketal oxygen is directly bonded to Ar ¹ and the other is bonded directly to Ar ² ); R ¹¹ and R ¹² are selected from the group consisting of unsubstituted or substituted C _1-18 linear or branched alkyl, unsubstituted or substituted C _3-18 cycloalkyl, unsubstituted or substituted C _6-18 aryl, and unsubstituted or substituted C _3-18 heteroaryl. In some embodiments, the cyclic ketal is part of a cyclic structure comprising the structure:

Ar ¹ -OC (R ¹ ) (R ² ) -O-Ar ²

In other embodiments, cyclic ketals are not part of this ring structure.

The ester may represent the structure - (O) _a- (L ¹ ) _b -C (= O) -OR ¹³ wherein a is 0 or 1 and b is 0 or 1 provided that a is 1 Is 1; R ¹³ is an unsubstituted or substituted C _1-20 linear or branched alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, Phenylpropan-2-yl, 1,1-diphenylethan-1-yl, triphenylmethyl), unsubstituted or substituted C _3-20 cycloalkyl such as cyclopentyl, cyclohexyl, methylcyclohexane- 2-methylbicyclo [2.2.1] heptan-2-yl, 1-adamantyl, 2-methyladamantane- 2-yl), unsubstituted or substituted C _6-20 aryl such as phenyl, 1-naphthyl and 2-naphthyl, and unsubstituted or substituted C _3-20 heteroaryl, 2-pyridyl, 3-pyridyl, and 4-pyridyl); Wherein L ¹ is an unsubstituted or substituted C _1-20 linear or branched alkylene such as methane-1,1-diyl (-CH ₂ -), ethane-1,2-diyl (-CH ₂ CH ₂ -), ethane-1,1-diyl (-CH (CH ₃ ) -), propane-2,2-diyl (-C (CH ₃ ) ₂ -)), unsubstituted or substituted C _3-20 cycloalkyl Cyclohexanediyl, 1,4-cyclohexanediyl), unsubstituted or substituted C _6-20 arylene (for example, 1-cyclohexanediyl, 1-cyclohexanediyl, : 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,6-naphthylene), and unsubstituted or substituted C _3-20 heteroarylene (E.g., imidazo-2,4-ylene, 2,4-pyridylene, 2,5-pyridylene). In some embodiments, R ¹³ and L ¹ are covalently linked to each other to form a lactone. In some embodiments, R < ¹³ > is bonded to an adjacent ester oxygen atom via a tertiary carbon atom, for example,

Alternatively, the ester may represent the structure - (O) _c - (L ² ) _d --OC (═O) - R ¹⁴ where c is 0 or 1 and d is 0 or 1, provided that c Is 1, d is 1; R ¹⁴ is an unsubstituted or substituted C _1-20 linear or branched alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, Phenylpropan-2-yl, 1,1-diphenylethan-1-yl and triphenylmethyl), unsubstituted or substituted C _3-20 cycloalkyl such as cyclopentyl, cyclohexyl, 2-methylbicyclo [2.2.1] heptan-2-yl, 2-methyladamantan-2-yl), unsubstituted or substituted C _6-20 aryl Naphthyl, 2-naphthyl), and unsubstituted or substituted C _3-20 heteroaryl such as 2-imidazolyl, 4-imidazolyl, 2-pyridyl, ); Wherein L ² is an unsubstituted or substituted C _1-20 linear or branched alkylene such as methane-1,1-diyl (-CH ₂ -), ethane-1,2-diyl (-CH ₂ CH ₂ -), ethane-1,1-diyl (-CH (CH ₃₎ -), propane-2,2-diyl _{(-C (CH 3) 2 -} ), 2- methyl propane-1,2-diyl (- _{CH 2 C (CH 3) 2} -), diphenylmethylene _{(-C (C 6 H 5)} 2 -), 1- phenyl-methane-1,1-diyl _{(-CH (C 6 H 5)} -), 2 -phenyl-1,2-diyl propane _{(-CH 2 C (CH 3)} (C 6 H 5) -), 1,1- diphenylethane-l, 2-diyl _{(-CH 2 C (C 6 H} 5 ) ₂ ) -, unsubstituted or substituted C _3-20 cycloalkylene such as 1,1-cyclopentanediyl, 1,2-cyclopentanediyl, 1,1-cyclohexanediyl, 1,4-diyl, 4-methyladamantane-1,4-diyl), unsubstituted or substituted C _6-20 arylene (e.g., 1,3- 4-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,6-naphthylene), and unsubstituted or substituted C _3-20 heteroarylene such as imidazo- Ylene, 2,4-pyridylene, 2,5-pyridylene) Group. In some embodiments, R ¹⁴ and L ² are covalently linked to each other to form a lactone. Specific examples of esters having the structure - (O) _c - (L ² ) _{d -} OC (= O) - R ¹⁴ are as follows:

The lactone may have the structure:

Wherein e is 0 or 1; f is 0 or 1; g is 1, 2, 3 or 4 (specifically 2); R ⁵⁰ is selected from the group consisting of hydrogen, unsubstituted or substituted C _1-18 linear or branched alkyl, unsubstituted or substituted C _3-18 cycloalkyl, unsubstituted or substituted C _6-18 aryl, or unsubstituted or substituted C _3-18 heteroaryl; L ³ is an unsubstituted or substituted C _1-20 linear or branched alkylene such as unsubstituted or substituted C _3-20 cycloalkylene such as 1,1-cyclopentanediyl, 1,2-cyclopentane Cyclohexanediyl, 1,4-cyclohexanediyl), unsubstituted or substituted C _6-20 arylene (e.g., 1,3-phenylene, 1,4-phenylene, 1,4 Naphthylene, 1,5-naphthylene, 2,6-naphthylene), and unsubstituted or substituted C _3-20 heteroarylene such as imidazo-2,4-ylene, 2,4- , 2,5-pyridylene).

In some embodiments, at least 40 mole percent of the plurality of repeating units, at least one of Ar ¹ , Ar ^2, and Ar ³ is substituted by at least one hydroxyl. Within this range, the mole percent of recurring units in which at least one of Ar ¹ , Ar ^2, and Ar ³ is substituted by at least one hydroxyl is at least 70 mole percent, at least 90 mole percent, at least 95 mole percent, at least 98 mole Percent, or at least 99 mole percent.

In some embodiments, at least one of R ¹ , R ² , Ar ¹ , Ar ² and Ar ³ (if present) is substituted by hydroxyl in at least one repeat unit of the polymer. In some embodiments, at least one of R ¹ , R ² , Ar ¹ , Ar ² , and Ar ³ (if present) is substituted by hydroxyl at least 40 mole percent of the plurality of repeat units. In some embodiments, at least one of Ar ¹ , Ar ^2, and Ar ³ (if present) in 40 to 99 mole percent of the plurality of repeat units is substituted by hydroxyl, and from 1 to 60 mole percent of the plurality of repeat units , At least one of Ar &^lt; ^{1 >} , Ar &^lt; ^{2 >} and Ar < ³ > is substituted by an acetal or ketal. A preferred acetal is -OC (H) (R ⁵ ) -OR ⁶ , wherein R ⁵ is methyl and R ⁶ is cyclohexyl. In some embodiments, in each case Ar ¹ , Ar ² and Ar ³ are independently 1,3-phenylene or 1,4-phenylene.

When used in applications where the polymer is exposed to an acid to promote fragmentation, it may be desirable to exclude strong bonds to the acid between the Ar ¹ and Ar ² rings of the polymer. Thus, in some embodiments, Ar < ^{1 >} and Ar < ² > are not covalently linked to each other through strong bonds to the acid to form a ring structure comprising -Ar ¹ -OCO-Ar ² -.

Specific examples of Ar ¹ , Ar ² and Ar ³ include unsubstituted or substituted 1,2-phenylene, unsubstituted or substituted 1,3-phenylene, unsubstituted or substituted 1,4-phenylene, Unsubstituted or substituted 4,4'-biphenylene, unsubstituted or substituted 4,4'- p -terphenylene, unsubstituted or substituted 3,3'- p -terphenylene, unsubstituted or substituted 4 , 4 " -m -terphenylene, unsubstituted or substituted 4,4" -p -terphenylene, unsubstituted or substituted 4,4'- o -terphenylene, unsubstituted or substituted 2,2 "- o -terphenylene, unsubstituted or substituted 1,4-naphthylene, unsubstituted or substituted 2,7-naphthylene, unsubstituted or substituted 2,6-naphthylene, unsubstituted or substituted 1 , 5-naphthylene, unsubstituted or substituted 2,3-naphthylene, unsubstituted or substituted 1,7-naphthylene, unsubstituted or substituted 1,8-naphthylene, unsubstituted or substituted imidazo- 2,4-diylene, 2,4-pyridylene, 2,5-pyridylene, Unsubstituted or substituted 9,10-anthracenylene, unsubstituted or substituted 2,7-phenanthrenylene, unsubstituted or substituted 9,10-phenanthrenylene, unsubstituted Unsubstituted or substituted 3,6-phenanthrenylene, unsubstituted or substituted 2,7-pyrenylene, unsubstituted or substituted 1,6-pyrenylene, unsubstituted or substituted 1,8-pyrenylene, Unsubstituted or substituted 3, 5-furanylen, unsubstituted or substituted 3,4-furanylen, unsubstituted or substituted 2,3-furanylen, unsubstituted or substituted 2,5-thiopyranylen, unsubstituted or substituted Thiopyranylene, unsubstituted or substituted 2,3-thiopuranylene, unsubstituted or substituted 2,5-oxazolylene, unsubstituted or substituted 2,7-fluorenylenylene, Substituted or unsubstituted 5,7-benzofuranylenes, unsubstituted or substituted 2,7-benzofuranylenes, unsubstituted or substituted 5,7-benzofuranylenes, unsubstituted or substituted 5,7- [1,3 - benzoxazole], Unsubstituted or substituted dithieno [3,2-b: 2 ', 3'-d] thiophene, and unsubstituted or substituted 2,7-xanthenylene. In some embodiments, in each case Ar ¹ , Ar ² and Ar ³ (if present) are independently 1,3-phenylene or 1,4-phenylene.

Ar < ^{1 >} and Ar < ² > are covalently linked to each other via the -OCO- bond of the acetal. In some embodiments, Ar ¹ and Ar ² are covalently linked to each other to form a ring structure comprising -Ar ¹ -OCO-Ar ² -. In some embodiments, Ar ¹ and Ar ² are not further covalently linked to one another to form a ring structure comprising -Ar ¹ -OCO-Ar ² -. That is, Ar ¹ and Ar ² Are covalently linked only through the -OCO- linkage of the acetal.

In polymer repeat units, R ¹ and R ² are each independently selected from the group consisting of hydrogen, unsubstituted or substituted C _1-18 linear or branched alkyl such as methyl, ethyl, 1-propyl, 2-propyl, Propyl, diphenylmethyl, 2-phenylpropan-2-yl, 1,1-diphenylethan-1-yl and triphenylmethyl), unsubstituted or substituted C _3-20 Cycloalkyl (e.g., cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantryl, 2-methylbicyclo [2.2.1] heptan-2-yl, 2-methyladamantan-2-yl); An unsubstituted or substituted C _6-18 aryl such as phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, or an unsubstituted or substituted C _3-18 heteroaryl such as 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl); R ¹ and R ² are optionally covalently linked mutually to form a ring containing -R ¹ -CR ² -.

를 들 수 있다.In some embodiments, at least one of R < ¹ > and R < ² > is hydrogen or methyl. In some embodiments, R ¹ is hydrogen and R ² is selected from phenyl, ortho-methoxyphenyl, meta-methoxyphenyl, and para-methoxyphenyl. In some embodiments, R ¹ is hydrogen and R ² is unsubstituted or substituted phenyl. When R < ² > is substituted phenyl, it is not compatible with polyacetal formation through hydroxyl groups, acetal groups, ester groups (including lactones), or acetal-generating polycondensation, or other such Lt; / RTI > group. As described in the co-filed application, the present inventors have confirmed that they can withstand the Suzuki polycondensation reaction in which polyacetal is synthesized from such gigabase (aryl) acetals. Two specific examples of polymer repeating units in which R ¹ and R ² are covalently linked to each other to form a ring containing the structure -R ¹ -CR ² -

.

내에서 서브구조

는 하기로 구성된 그룹 중에서 선택된다:In some embodiments, any repeating unit

Substructure within

Is selected from the group consisting of:

내에서 서브구조

는 하기로 구성된 그룹 중에서 선택된다:In some embodiments, any repeating unit

Substructure within

Is selected from the group consisting of:

In some embodiments, the polymer is end-capped with a terminal group -Ar ⁴ wherein each Ar ⁴ is independently selected from unsubstituted or substituted C _6-18 arylene, or unsubstituted or substituted _{Lt; /} RTI > heteroarylene. Specific examples of Ar < ⁴ > include:

In some embodiments, at least one end-capping agent in the form of Ar ⁴ -X or Ar ⁴ -B ^x (where X and B ^x are as defined above) is (1) reduced in the halogen and / or boron content of the polymer / (2) added after completion of the polymerization reaction as a method for controlling the polymer properties including solubility and substrate adhesion. In some embodiments, the suitable amount of endcapping agent is from 0.01 to 5 equivalents relative to the initial monomer concentration, specifically from 0.1 to 0.3 equivalents relative to the initial monomer concentration.

In some embodiments, at least one end-capping agent in the form of Ar ⁴ -X or Ar ⁴ -B ^x (where X and B ^x are as defined above) is (1) limited in molecular weight and / or (2) To reduce / reduce the halogen and / or boron content of the final polymer, and (3) to control specific polymer properties including solubility and substrate adhesion. Suitable amounts of the endcapping agent depend on the relative molecular reactivity of the endcapping agent compared to the desired molecular weight and / or monomer reactivity and range from 0.0001 to 1 equivalent based on the initial monomer concentration.

In some embodiments, the polymer comprises a plurality of repeating units having the structure:

Wherein one R ²¹ is hydroxyl and the other three R ²¹ is hydrogen; Two R < ²¹ > are hydroxyl and the other two R < ²¹ > are hydrogen; Three R < ²¹ > are hydroxyl and the other R < ²¹ > is hydrogen; All four R &^lt; ²¹ > are hydroxyl; Any of the R < ²¹ >, which is a hydroxyl, may instead be an acetal or an ester;

Wherein one R ²¹ is hydroxyl and the other three R ²¹ is hydrogen; Two R < ²¹ > are hydroxyl and the other two R < ²¹ > are hydrogen; Three R < ²¹ > are hydroxyl and the other R < ²¹ > is hydrogen; All four R &^lt; ²¹ > are hydroxyl; Any of the R < ²¹ >, which is a hydroxyl, may instead be an acetal or an ester; In some embodiments, the polymer comprises a plurality of repeating units selected from:

(Wherein R ¹⁰¹ is hydrogen or hydroxyl, R ¹⁰² is a hydroxyl or when R ¹⁰¹ is hydrogen, R ¹⁰² is R ¹⁰¹ is a hydroxyl silil when a hydrogen);

이다);Wherein R ²⁰¹ is hydrogen or -OCHVE, R ²⁰² is hydrogen when R ²⁰¹ is hydrogen, or when R ²⁰¹ is -OCHVE, wherein -OCHVE is

to be);

(Wherein R ³⁰¹ is a -OC (= O) -CH ₃ (acetate) or -OCHVE, R ³⁰² is -OCHVE or when R ³⁰¹ is -OC (= O) -CH ₃ (acetate), R ³⁰¹ is -OCHVE is -OC (= O) -CH ₃ (acetate) when);

(Wherein R ⁴⁰¹ and R ⁴⁰² are each independently hydroxyl or -OCHVE);

Wherein R ⁵⁰¹ is hydrogen or hydroxyl, R ⁵⁰² is hydroxyl when R ⁵⁰¹ is hydrogen, or R ⁵⁰² is hydrogen when R ⁵⁰¹ is hydroxyl;

(Wherein R ⁶⁰¹ is hydrogen or -OCHVE, R ⁶⁰² is -OCHVE when R ⁶⁰¹ is hydrogen, or hydrogen when R ⁶⁰¹ is -OCHVE);

Wherein R ⁷⁰¹ is hydrogen or hydroxyl, R ⁷⁰² is hydroxyl when R ⁷⁰¹ is hydrogen, or R ⁷⁰² is hydrogen when R ⁷⁰¹ is hydroxyl;

(Wherein R ⁸⁰¹ is hydrogen or -OCHVE, R ⁸⁰² is -OCHVE when R ⁸⁰¹ is hydrogen, or hydrogen when R ⁸⁰¹ is -OCHVE);

Wherein R ⁹⁰¹ is hydrogen or hydroxyl, R ⁹⁰² is hydroxyl when R ⁹⁰¹ is hydrogen, or R ⁹⁰² is hydrogen when R ⁹⁰¹ is hydroxyl;

(Wherein R ¹⁰⁰¹ is hydrogen or -OCHVE, R ¹⁰⁰² is hydrogen when R ¹⁰⁰¹ is hydrogen, or R ¹⁰⁰¹ is -OCHVE);

;

;

Wherein R ¹¹⁰¹ is hydrogen or -O-CH ₂ -C (= O) -O-Ad and R ¹¹⁰² is -O-CH ₂ -C (= O) -O-Ad when R ¹¹⁰¹ is hydrogen , And R ¹¹⁰¹ is -O-CH ₂ -C (═O) -O-Ad, wherein -CH ₂ -C (═O) -O-Ad is

;

;

;

;

;

;

;

;

;

;

;

;

And combinations thereof).

Specific examples of the polymer include the following structures

A polymer comprising a repeating unit of (wherein R ¹⁰¹ is hydrogen or hydroxyl, R ¹⁰² is a hydroxyl or when R ¹⁰¹ is hydrogen, R ¹⁰² is R ¹⁰¹ is a hydroxyl silil when a hydrogen);

The following structure

(Wherein R ¹⁰¹ is hydrogen or hydroxyl, R ¹⁰² is hydroxyl when R ¹⁰¹ is hydrogen, or R ¹⁰² is hydrogen when R ¹⁰¹ is hydroxyl) 99 mole percent), and the following structures

이다)의 반복 단위(바람직하게 총 반복 단위의 1 내지 40 몰퍼센트의 양으로)를 포함하는 중합체;(R ²⁰¹ is hydrogen or -OCHVE, R ²⁰² is hydrogen when R ²⁰¹ is hydrogen, or when R ²⁰¹ is -OCHVE, wherein -OCHVE is

) (Preferably in an amount of from 1 to 40 mole percent of the total repeating units);

The following structure

(Wherein R ³⁰¹ is a -OC (= O) -CH ₃ (acetate) or -OCHVE, R ³⁰² is -OCHVE or when R ³⁰¹ is -OC (= O) -CH ₃ (acetate), R ³⁰¹ is polymers comprising repeating units of one when -OCHVE is -OC (= O) -CH ₃ (acetate));

The following structure

(Wherein R ⁴⁰¹ and R ⁴⁰² are each independently a hydroxy or a thiol -OCHVE, preferably R ⁴⁰¹ and from about 1 to about 70 mole percent of the total number of moles of R ⁴⁰² is -OCHVE, the total number of moles of R ⁴⁰¹ and R ⁴⁰² ≪ / RTI > 60 to 99 mole percent of the hydroxyl group is hydroxyl);

The following structure

(Wherein R ⁵⁰¹ is hydrogen or hydroxyl, R ⁵⁰² is hydroxyl when R ⁵⁰¹ is hydrogen, or R ⁵⁰² is hydrogen when R ⁵⁰¹ is hydroxyl) 99 mole percent), and the following structures

(R ⁶⁰¹ is hydrogen or -OCHVE, and R ⁶⁰² is a hydrogen atom when R ⁶⁰¹ is hydrogen or -OCHVE or when R ⁶⁰¹ is -OCHVE) repeating units (preferably 1 to 40 mole percent of total repeating units ≪ / RTI >

The following structure

(Wherein R ⁷⁰¹ is hydrogen or hydroxyl, R ⁷⁰² is hydroxyl when R ⁷⁰¹ is hydrogen, or R ⁷⁰² is hydrogen when R ⁷⁰¹ is hydroxyl) 99 mole percent), and the following structures

(R ⁸⁰¹ is hydrogen or -OCHVE, and R ⁸⁰² is a hydrogen atom when R ⁸⁰¹ is hydrogen or -OCHVE or when R ⁸⁰¹ is -OCHVE), preferably 1 to 40 mole percent of total repeating units ≪ / RTI >

The following structure

(Wherein R ⁹⁰¹ is hydrogen or hydroxyl, R ⁹⁰² is hydroxyl when R ⁹⁰¹ is hydrogen, or R ⁹⁰² is hydrogen when R ⁹⁰¹ is hydroxyl) 99 mole percent), and the following structures

⁽¹⁰⁰¹ R is hydrogen or -OCHVE, R ¹⁰⁰² R ¹⁰⁰¹ is a -OCHVE or when hydrogen, R is hydrogen when -OCHVE ¹⁰⁰¹⁾ the repeating unit (preferably an amount of from 1 to 40 mole percent of repeating units of ≪ / RTI >

The following structure

And the following structure

를 나타난다)의 반복 단위를 포함하는 중합체; Wherein R ¹¹⁰¹ is hydrogen or -O-CH ₂ -C (= O) -O-Ad and R ¹¹⁰² is -O-CH ₂ -C (= O) -O-Ad when R ¹¹⁰¹ is hydrogen , Where R ¹¹⁰¹ is -O-CH ₂ -C (= O) -O-Ad, where -CH ₂ -C (= O) -O-

Lt; RTI ID = 0.0 > of: < / RTI >

The following structure

And the following structure

Lt; / RTI >;

The following structure

And the following structure

Lt; / RTI >;

The following structure

And the following structure

And the following structure

Of repeating units.

In a very specific embodiment, the polymer comprises a plurality of repeating units having the following structure

Wherein in each case Ar < ¹ > and Ar < ² > are 1,4-phenylene; Ar ³ is an alkylene unsubstituted or substituted 1,3-phenylene in each case, where Ar ³ in at least 40 mole percent of the plurality of repeating units is substituted by at least one hydroxyl; In each case R ¹ is hydrogen; In each case R < ² > is phenyl.

Polymers may be used in biologic applications such as pH-dependent delivery of active agents including pharmaceuticals, prodrugs and amplified drug release, microencapsulation and prolonged release applications such as encapsulation of active agents in the case of pharmaceutical or pesticidal applications ); Diagnostic application; Signal amplification; Lithography, e.g., photolithography for lithography using ultraviolet (UV) wavelengths, extreme ultraviolet wavelengths (EUV) and electron beams, photoresist topcoats and underlayers; Electronic devices such as patterned light emitting devices (OLED / PLED), photovoltaic devices, organic thin film transistors (TFTs), and molecular logic gates; Detection or imaging of photographic applications, such as radioactive compounds or UV radiation; ≪ / RTI > and pH markers.

Figure 1 shows the polymer backbone and side chain breakdown of the polymer pBEBA-2,4-DBP-CHVE of Example 8 after treatment with dilute aqueous triflic acid.
Figure 2 shows that acid treatment of the polymer significantly affects its solubility characteristics.

The present invention is further illustrated by the following examples.

All solvents and reagents were obtained in commercially available quality, purum, puriss or pa (pa). Dry solvents were either obtained from an internal refining / dispensing system (hexane, toluene, tetrahydrofuran and diethyl ether) or from a company (Sigma-Aldrich, Disher Scientific, or Acros). All experiments involving water sensitive compounds were carried out in a glass apparatus dried in an oven under a nitrogen atmosphere or in a glove box. The reaction was monitored by analytical thin layer chromatography (TLC) on a precoated aluminum plate (VWR 60 F254) and visualized by UV light and / or potassium permanganate staining. Flash chromatography was performed on an Isco COMBIFLASH ^TM system using a GRACERESOLV ^TM cartridge.

Unless otherwise stated, proton nuclear magnetic resonance ( ¹ H-NMR) spectra (500 MHz or 400 MHz) were obtained on a Varian VNMRS-500 or VNMRS-400 spectrometer at 30 ° C. Chemical shifts in CDCl ₃ with tetramethylsilane (TMS) (δ = 0.00) , benzene - benzene in d ₆ - d ₅ (7.15) or THF- d ₈ of tetrahydrofuran _{-d 7 (THF- d 7; δ} 3.58 (used) and 1.73). Peak assignments were performed with the help of COZY, HSQC or NOESY experiments, if necessary. ^{The 13} C-NMR spectra (125 MHz or 100 MHz) were obtained on a Varian VNMRS-500 or VNRMS-400 spectrometer and the chemical shifts were determined using a solvent or standard signal (TMS in 0.0-CDCl ₃ , 128.02-benzene- d ₆ , 67.57 ) -THF- d ₈ ). When using NMR for quantitative purposes, a single scan experiment or a relaxation delay time of ≥ 30 sec was used.

Except as otherwise noted, high resolution mass spectrometry was performed as follows. For a liquid chromatography (ESI / LC / MS / MS) study coupled with electrospray ionization mass spectrometry (ESI / MS) and electrospray ionization tandem mass spectrometry, as a 1 milligram / milliliter solution in methanol, Agilent 1200SL binary gradient liquid chromatography coupled with Agilent 6520 QToF, a quadrupole-time of flight MS system via a dual atomization electrospray (ESI) interface operating in a PI mode of the lighter aliquot . The following assay conditions were used: Column: non-flow injection; Column temperature: 40 占 폚; Mobile phase: 0.3 M ammonium acetate in methanol; Flow rate: 0.25 milliliters / min; UV detection: Diode array 210 to 600 nanometers; ESI conditions: gas temperature - 350 ° C, gas flow rate - 8 milliliters / min, capillary - 3.5 kV, atomizer - 45 pounds per square inch, fragmentor - 145 V; Auto MSMS Condition: Mode - ± / TOFMS and ± TOFMSMS; Centroid Resolution 12000 (+) 2 gigahertz extended dynamic range, scan-100 to 1700 atomic mass units (± MS), velocity-4 Atomic mass units (± MS / MS), velocity - 4 scans / second, collision energy: 5V + 5V / 100 atomic mass unit, collision gas: nitrogen, separation width ~ 4 atomic mass unit , Reference ion: 121.050873: 922.009798 (+); 112.985587, 1033.988109. In the high-resolution gas chromatography / mass spectrometry (GC / MS) For R, a voice chemical ionization of the sample 1 microliter as a 3 mg / ml solution in methylene chloride (using ammonia as the reactant gas) (NCI-NH ₃₎ mode Agilent 7200 QToF, quadrupole-flight time MS system coupled to an Agilent 7890A gas chromatograph. The following analytical conditions were used: Column: 30 m x 0.25 mm (0.25 micrometer film) HP-5MS, temperature: column - 120 deg. C (2 min) to 320 deg. Injector - 300 ℃; Interface - 300 ℃; Sources - 165 ° C (CI); Flow rate: linear velocity - constant flow rate of 1.2 milliliters / minute; Split-130: 1; Detector: Mode - + TOFMS, CENT; Resolution - 10000; 2Ghz extended dynamic range; Electronic energy - 150 eV (CI); Scanning - 165 to 900 atomic mass units (-CI); Speed - 5 scans / second; CI gas: Ammonia flow rate 40.

Infrared spectra were acquired using the PerkinElmer Spectrum One FT-IR and Universal ATR Sampling Accessories at nominal resolutions of 4 centimeters ^-1 and 16 scans (approximate acquisition time of 90 seconds). Universal ATR sampling accessories are equipped with a single bounce diamond / ZnSe crystal.

The melting point (T _m ) and the glass transition temperature (T _g ) were measured by a differential scanning calorimeter (DSC) using TA Instruments Q2000 DSC using T4 calibration (indium, sapphire). Approximately 5 milligrams of each sample was weighed into a TZero aluminum DSC pan with lid. The heating: cooling: heating temperature profile at a ramp rate of 10 [deg.] C / min under nitrogen purge was used. The sample was heated from room temperature to 150 占 폚, cooled to -90 占 폚 and again heated to 150 占 폚. Data analysis was performed using TA universal analysis software.

The number average molecular weight (M _n ), weight average molecular weight (M _w ) and polydispersity (D = M _w / M _n ) of the polymer were measured by gel permeation chromatography. Two milligrams of the polymer sample was dissolved in 1.0 milliliter of undissolved THF, followed by 0.22 micrometer membrane filtration, and 50 microliters of the obtained sample was injected into an Agilent 1100 series GPC system coupled with a refractive index detector. The following analytical conditions were used: Column: 300 x 7.5 mm Agilent PLgel 5 mu m MIXED-C Column temperature 35 DEG C Mobile phase THF Flow rate 1 milliliter per minute Detector temperature 35 DEG C

The thermal decomposition temperature (T _d ) was measured by thermogravimetric analysis (TGA) on a TA instrument Q5000IR with an infrared accessory and autosampler. Approximately 5 milligrams of each sample was weighed into a TA hot platinum pan. The sample was loaded at room temperature (using an autosampler) and heated to 600 ° C at 10 ° C / min under constant dry air purge. Data analysis was performed using TA universal analysis software.

Production Example 1

[1- (cyclohexyloxy) ethoxy] -2,5-dibromophenol. To a solution of 2,4-dibromophenol (10.0 grams, 39.6 millimoles, 1.2 equivalents) and cyclohexyl vinyl ether (4.69 milliliters, 33.0 millimoles, 1.0 equiv) in toluene (50 milliliters) under nitrogen, 0.25 milliliters (3.30 millimoles, 0.10 eq.) Of trifluoroacetic acid were added. The reaction was stirred overnight at room temperature (18-24 h). Triethylamine (1.38 mL, 9.92 mmol, 0.3 eq.) Was added, stirred for 5 minutes, and concentrated to post-treat the reaction mixture. The resulting oil was taken up in 50 milliliters of hexane and filtered through a basic alumina plug. The plug was washed with 1.4 liters of a 1: 1 solution of hexane and diethyl ether. The solvent was removed from the rotary evaporator and the resulting oil was further dried under high vacuum for at least 24 hours. The product was obtained in 75% yield (9.35 grams, 24.7 mmol) as a racemate in the form of a colorless oil. ^{1 H NMR (500 MHz, CDCl} 3) δ 7.67 (d, J = 2.4 Hz, 1H), 7.33 (dd, J = 8.8, 2.4 Hz, 1H), 7.05 (d, J = 8.8 Hz, 1H), 5.47 (q, J = 5.3 Hz, 1H), 3.68 (tt, J = 9.3, 3.9 Hz, 1H), 1.97 - 1.63 (m, 4H), 1.55 - 1.48 (m, 1 H), 1.51 (d, J = 5.3 Hz, 3H), 1.43-1.33 (m, 1H), 1.33-1.12 (m, 4H). ¹³ C NMR (126 MHz, CDCl ₃ ) 隆 152.63, 135.50, 131.04, 119.73, 115.19, 114.34, 99.76, 74.94, 33.41, 32.28, 25.52, 24.19, 24.02, 20.72. FTIR (thin film): 595, 641, 670, 689, 719, 782, 796, 817, 867, 891, 906, 959, 979, 1022, 1038, 1069, 1141, 1232, 1242, 1261, 1280, 1344, 1376 , 1450, 1469, 1578, 2856, 2932, 2991 cm < ^{-1 &} gt ;; UV / Vis: 225 (shoulder), 238, 286 nm; HRMS (GC / MS / NCI- NH3): 374.95735, C 14 H 17 calculated for _{Br 2 O 2 [MH] 374.9601} , found 374.9591.

Production Example 2

4,6-dibromo-1,3-benzenediol. This synthesis was adapted to the method of Shoji Kajigaeshi, Takaaki Kakinami, Tsuyoshi Okamoto, Hiroko Nakamura, Masahiro Fujikawa, Bulletin of the Chemical Society of Japan , 1987, volume 60, pages 4187-4189. Pyridinium tribromide (29.0 grams, 90.8 mmol, 2.0 eq.) Was added to a solution of resorcinol (5.00 grams, 45.4 mmol, 1.0 eq.) Dissolved in 100 milliliters of dichloromethane and 40 milliliters of methanol for 60-70 min Were added in small quantities throughout the process. The reaction solution was stirred overnight at room temperature. The solvent was removed from the rotary evaporator and the residue was taken up in chloroform (1 x 50 milliliters) and re-concentrated. Ethyl acetate was added to precipitate byproducts. The ethyl acetate phase was decanted and the precipitate was washed several more times (4 x 150 mL 1: 1 ether / ethyl acetate, 1 x 150 mL ethyl acetate, decanted solvent). The decanted solvents were combined, concentrated and then purified by automated flash chromatography (methanol in chloroform, 0-15%). The product was obtained in the form of a pale yellow solid (10.9 grams, 40.7 mmol, 90%). Melting point: 66.4 占 폚; ¹ H-NMR (400 MHz, CDCl ₃ )? 7.53 (s, 1H), 6.74 (s, 1H), 5.46 (s, 2H); ^& Lt; ¹³ > C NMR (101 MHz, THF-d8) [delta] 155.60, 136.10, 105.13, 100.74, 67.57; FTIR: 569, 594, 659, 742, 837, 868, 993, 1053, 1138, 1193, 1282, 1326, 1440, 1462, 1494, 1577, 1598, 1711, 2918, 3089, 3379, 3451, 3504 cm -1 ; UV / Vis: 223, 236, 296 nm; ESI / MS / MS on m / z = 267: 267 [ M 79Br / 81Br -H] -, 188 [M 81Br- HBr)] -, 186 [M 79Br- HBr)] -, _{160 [M 81Br- HBr-CO)} ] -, 158 [M 79Br- HBr-CO)] -, 81 [81 Br] -, 79 [79 Br] -; ^{HRMS (ESI -): 374.95735,} C 6 H 3 Br 2 O 2 - [MH] - calculated for 264.8505, found 264.8510.

Production Example 3

[1,3-bis (cyclohexyloxy) ethoxy] -2,5-dibromore resorcinol. Dissolve 2,4-dibromo-resorcinol (10.5 grams, 39.1 mmol, 1.0 eq) and cyclohexyl vinyl ether (11.3 milliliters, 80.1 mmol, 2.05 eq.) In toluene (100 milliliters) Trifluoroacetic acid (0.30 mL, 3.91 mmol, 0.10 eq) was added. The mixture was stirred at room temperature overnight (18-24 h). The reaction was quenched by the addition of triethylamine (1.63 milliliters, 11.7 mmol, 0.3 eq) and concentrated. The resulting oil was taken up in hexane (50 milliliters), filtered through a plug of basic alumina, and the product was completely eluted with additional hexane (~ 1 liter). The solvent was removed from the rotary evaporator and the product obtained was further dried under high vacuum for at least 24 hours. The title compound was obtained (16.1 grams, 30.9 mmol, 79%) as a racemic mixture of diastereomers in the form of slightly yellowish oil. ¹ H-NMR (400 MHz, CDCl ₃ )? 7.67 (s, 0.47H (diast. A)), 7.67 (s, 0.53H A, b), 5.46 (q, J = 5.3 Hz, 2H, diast. A, b), 3.75-3.65 b), 1.55-1.48 (m, 2H), 1.51 (d, J = 5.3 Hz, 2.82H (diast.a)), 1.51 (d, J = 5.3 Hz, 3.13H - 1.12 (m, 10H); ^{13 C NMR (101 MHz, THF} -d8) δ 155.09 (diast. B), 155.05 (diast. A), 137.22 (diast. A?), 137.20 (diast. B?), 110.60 (diast. B), 110.40 (diast. a), 107.64 (diast. b), 107.54 (diast.a), 101.35 (diast.??), 101.31 (diast. b?), 35.17 (diast.?), 33.99 (diast. b?), 33.97 (diast. a?), 27.38 a).

Production Example 4

2,4-dibromo-5-hydroxyphenylacetate. (10.58 grams, 39.5 millimoles, 1.0 equivalents) and triethylamine (11.0 milliliters, 7.99 grams, 79.0 millimoles, 1.0 grams) dissolved in dichloromethane (80 milliliters) 2.0 eq) was cooled to 0 < 0 > C. Acetyl chloride (3.09 milliliters, 43.4 mmol, 1.1 eq.) Was added over a 17 minute course. The reaction solution was warmed to room temperature and stirred overnight. Volatile materials were removed by rotary evaporation and the reaction solution was post-treated. The solid residue was taken up in 100 milliliters of ethyl acetate. The mixture was stirred for 5 minutes and filtered to remove the precipitate. The product was purified by gradient flash column chromatography (ethyl acetate in hexanes, 0-40%). The product was obtained in the form of a colorless solid (6.73 grams, 21.7 mmol, 55%). Melting point: 121.3 캜; ^{1 H-NMR (400 MHz,} CDCl 3) δ 7.69 (s, 1H), 6.85 (s, 1H), 5.59 (s, 1H), 2.34 (s, 3H); ¹³ C NMR (101 MHz, THF)? 168.12, 155.60, 149.52, 136.49, 112.77, 108.40, 106.30, 20.59; FTIR 570, 647, 690, 707, 768, 842, 872, 920, 1025, 1060, 1168, 1206, 1240, 1367, 1394, 1489, 1580, 1599, 1718, 2936, 2993, 3082, 3296 cm ^-1 ; UV / Vis: 221, 229 (overlap), 292 nm; The ESI / MS / MS m / z = 309: 309 [M 79Br / 81Br -H] -, 267 [M 79Br / 81Br - (CH 2 C = O, H)] -, 81 [81 Br] -, 79 [ ⁷⁹ Br] ^- ; _{^{HRMS (ESI -): C 8}} H 5 Br 2 O 3 - [MH] - calculated for 306.8605, found 306.8622.

Production Example 5

2,4-dibromo-5- (1- (cyclohexyloxy) ethoxy) phenylacetate. Under nitrogen, 2,4-dibromo-5-hydroxyphenylacetate (4.00 grams, 12.9 mmol, 1.0 eq.) And cyclohexyl vinyl ether (2.74 mL, 19.3 mmol, 1.5 eq.) Were dissolved in toluene (50 mL) . Trifluoroacetic acid (0.10 mL, 1.29 mmol, 0.10 eq.) Was added and the mixture was stirred at room temperature overnight (18-24 h). Triethylamine (0.53 mL, 3.87 mmol, 0.3 eq.) Was added to quench the reaction and the volatiles were removed on a rotary evaporator. The resulting oil was taken up in diethyl ether (30 milliliters) and filtered through a plug of basic alumina. The product was rinsed with additional ether (500 milliliters). The solvent was removed from the rotary evaporator and the resulting oil was pumped over 24 hours. The product was obtained as racemate in the form of slightly yellowish oil (3.77 grams, 8.64 mmol, 67%). ^{1 H NMR (400 MHz, CDCl} 3) δ 7.76 (s, 1H), 7.00 (s, 1H), 5.48 (q, J = 5.4 Hz, 1H), 3.69 (tt, J = 9.1, 3.9 Hz, 1H) , 2.34 (s, 3H), 1.94-1.63 (m, 4H), 1.55-1.48 (m, 1H), 1.52 (d, J = 5.3 Hz, 3H), 1.44-1.02 (m, 5H); ¹³ C NMR (101 MHz, THF- d8 ) δ 168.19, 154.65, 149.40, 136.68, 114.35, 111.79, 108.79, 100.94, 75.66, 34.45, 33.33, 26.69, 24.97, 24.85, 20.94, 20.55; FTIR (film): 647, 703, 725, 840, 891, 979, 1018, 1059, 1170, 1190, 1248, 1279, 1368, 1393, 1466, 1584, 1779, 2856, 2932 cm ^-1 ; UV / Vis 223, 232 (overlap), 290 nm; M / z of ESI / MS / MS = 459: 459 [M _{79 Br / 81 Br} + Na] ⁺ , 341, 281, 207, 151, 109 83 [C ₆ H ₁₁ ] ⁺ ; _{^{HRMS (ESI +): C 16}} H 20 Br 2 NaO 4 + calculated for [M ⁺ Na] + 456.9621, found 456.9628.

Production Example 6

4,4 '- ((Phenylmethylene) bis (oxy)) bis (bromobenzene). To a solution of 4-bromophenol (12.0 grams, 69.4 mmol, 2.5 eq) dissolved in anhydrous 1-methyl-2-pyrrolidinone (100 milliliters) in a nitrogen-purged glove box was added 95% sodium hydride (1.82 grams, 72.1 mmol, 2.6 eq.) Was added portionwise over a period of 30 min. The reaction solution was stirred at room temperature for an additional 90 minutes. α, α-Dichlorotoluene (4.13 milliliters, 27.7 mmol, 1.0 equivalent) was added and the reaction was heated to 70 ° C. overnight. The reaction was quenched by adding to water (200 milliliters). The aqueous phase was extracted with a 1: 1 mixture of diethyl ether and ethyl acetate (3 x 120 mL). The organic phases were combined and then washed with deionized water (5 x 100 milliliters), brine (1 x 100 milliliters) and dried over magnesium sulphate. After filtration and concentration on a rotary evaporator, the residue was taken up in diethyl ether (60 milliliters) and filtered through a plug of basic alumina. Additional diethyl ether (700 milliliters) was used to completely elute the product and concentrate on a rotary evaporator. After further drying under high vacuum for several days, the product in the form of a yellow oil was quantitatively obtained which crystallized over time to give a yellowish white solid (12.0 grams, 27.7 mmol, 100%). Melting point: 50.8; ¹ H-NMR (400 MHz, CDCl ₃ )? 7.59 - 7.51 (m, 2H), 7.44-7.37 (m, 3H), 7.37-7.29 s, 1H); ¹³ C-NMR (101 MHz, CDCl ₃ ) 隆 155.07, 136.58, 132.59, 129.65, 128.86, 126.78, 119.60, 115.42, 100.77; FTIR: 605, 658, 674, 694, 741, 792, 816, 848, 886, 928, 984, 1031, 1060, 1100, 1115, 1167, 1178, 1210, 1242, 1280, 1304, 1363, 1449, 1483, 1584, 1689, 3033, 3065 cm < ^{-1 &} gt ;; UV / Vis 223 (shoulder), 237, 278 nm; GC / MS / EI ^& lt ^{; +} & gt ^; : 432, 434, 436 [M ^< ⁺ &^gt;] (2xBr isotope pattern); _{261, 263 [Br-C 6} H 4 -O-CHPh] + (1 × Br isotope pattern); _{182 [C 6 H 4 -O-} CHPh] +; _{^{HRMS (ESI -): C 19}} H 13 Br 2 O 2 - [M + Na] ⁺ calcd for 430.9288, found 430.9287.

Preparation Example 7

Bis (4,1-phenylene)) - bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane ). (12.0 grams, 27.6 mmol, 1.0 eq.) Of 4,4 '- ((phenylmethylene) bis (oxy)) bis (bromobenzene) in anhydrous THF (120 milliliters) 78 Lt; 0 > C. n-Butyllithium (1.6 M in hexane, 42 mL, 65.5 mmol, 2.4 eq.) was added over 60 min. The reaction solution was stirred at -78 占 폚 for 90 minutes. 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17 milliliters, 83.1 mmol, 3.00 eq.) Was added dropwise to the reaction solution over a period of 30 minutes. The reaction solution was warmed to room temperature overnight. Water (2 milliliters) was added dropwise, the reaction was carefully quenched and stirred for 10 minutes. Dichloromethane (200 milliliters) was added and the reaction mixture was dried over magnesium sulfate. The solids were filtered and the organic phase was concentrated. The residue was dissolved in dichloromethane (100 milliliters) and filtered through a silica plug covered with a layer of CELITE ( ^TM) diatomaceous earth. The product was completely eluted with additional dichloromethane (400 milliliters) and the organic phases were combined and concentrated. The silica plug filtration process was repeated two more times. After final concentration, the residue was recrystallized to the minimum amount of boiling acetonitrile, which was gradually cooled to 5 < 0 > C overnight. The colorless crystals were separated by filtration, washed with a small amount of cold acetonitrile, and dried overnight under vacuum at 65 < 0 > C. The final product was obtained in 70% yield (10.2 grams, 19.3 mmol). ¹ H-NMR (400 MHz, CDCl ₃ )? 7.72-7.66 (m, 4H), 7.63-7.58 (m, 2H), 7.43-7.55 s, 1 H), 1.31 (s, 24 H); ^{13 C NMR (101 MHz, cdcl} 3) δ 158.67, 137.10, 136.46, 129.27, 128.62, 126.69, 116.53, 99.72, 83.63, 24.86, 24.85 ( one overlapping peak of a); FTIR: 578, 632, 651, 697, 733, 756, 832, 855, 884, 919, 964, 996, 1065, 1084, 1096, 1141, 1173, 1210, 1247, 1272, 1322, 1359, 1400, 1458, 1573, 1604, 2927, 2977 cm < ^{-1 &} gt ;; UV / Vis: 242 nm; ^{ESI +: 549, 550, 551} , 552, 553 [M + Na] + (2 × B and isotope pattern consistent with the 31 × C), 308, 309 (bp), 310 [pinB-C 6 H 4 - O-CHPh] ⁺ (isotopic pattern consistent with B and 19 x C); HRMS (ESI ⁺ ): calcd for C ₃₁ H ₃₈ B ₂ NaO ₆ ⁺ [M + Na] ⁺ 551.2752, found 551.2762.

Production Example 8

pBEBA-2,4-DBP-CHVE (100%). (7.0 grams, 13.25 mmol, 1.00 eq.) And [1- (cyclohexyloxy) ethoxy] -2,5 dibromophenol (4.81 grams, 12.72 mmol) in a 500 mL round bottom flask under nitrogen. , 0.96 eq.) Were combined and dissolved in oxygen-free 1,4-dioxane (60 milliliters). (Different molecular weights can be synthesized by controlling the boronic acid ester to dihalide ratio using the Carothers equation as a guideline.) Under nitrogen, Pd ( t Bu ₃ ) is added to a separate vial P) Cl (5.2 mg, 13.3 micromoles, 0.001 eq.) Was dissolved in 1 milliliter of oxygen-free 1,4-dioxane. To another separate vial, under nitrogen, potassium phosphate (8.80 grams, 41.5 millimoles, 3.13 equivalents) was dissolved in 12.8 milliliters of degassed water. The potassium phosphate solution was added to the monomer solution and vigorously stirred. After the mixture was converted into a homogeneous emulsion, the catalyst solution was added and the reaction solution was stirred overnight at room temperature. Phenylboronic acid (242 mg, 1.99 mmol, 0.15 eq) was added and the mixture was stirred for 8 h. Bromobenzene (417 milliliters, 624 milligrams, 3.98 mmol, 0.30 eq) was added and the reaction was further stirred overnight. The reaction solution was separated and post-treated by discarding the water phase. The organic phase was concentrated in a rotary evaporator and taken up in ethyl acetate (~ 100 milliliters, some insoluble material was triturated). A saturated aqueous solution (~10 milliliters) of sodium diethyldithiocarbamate was added to a flask equipped with a reflux condenser and the mixture was vigorously stirred under reflux for 60 minutes. The organic phase was then separated and filtered through a silica plug covered with basic alumina. Additional ethyl acetate was used to elute the polymer (measured by TLC spotting), concentrated to about 50 milliliters and precipitated three times from methanol. The polymer was separated by filtration, washed with additional methanol and dried at 60 < 0 > C under high vacuum for several days. The polymer product was obtained in the form of a colorless fine powder (3.3 grams, 51% polymerization yield). DSC: T _g of 104.1 ℃; TGA: T _d (5% weight loss) at 208.0 캜; GPC (for the PMMA standard): M _n = 4.73 kilodalton (kDa), M _w = 8.60 kDa, D = 1.82; ¹ H NMR (400 MHz, THF- d ₈ )? 7.71-7.61 (6.7%), 7.54-7.45 (14.1%), 7.44-7.22 (12.6%), 7.21-7.15 %), 6.95-6.82 (3.5%), 5.67-5.07 (2.5%), 3.50-3.88 (2.7%), 2.47-2.45 (1.4%), 1.70-1.52 (12.4%), 1.45-1.02 ; ^{13 C NMR (101 MHz, THF-} d 8) δ 156.73, 156.63, 154.45, 139.11, 137.35, 135.96, 135.41, 134.05, 133.32, 131.73, 129.99, 129.84, 129.37, 128.56, 127.89, 127.86, 127.01, 118.82, 118.54 , 117.53, 117.23, 101.18, 100.27, 84.38, 75.08, 34.40, 33.25, 26.77, 25.02, 24.87, 21.72.

Production Example 9

및 페놀 양성자

의 적분비를 감시하여 탈보호화 진행을 산정하였다. 일단 아세탈 대 페놀의 적분비가 60:40으로 되면, 트리에틸아민(30 마이크로리터)을 가하여 반응을 켄칭하였다. 용매를 회전증발로 제거하였다. 얻어진 잔류물을 소량의 에틸 아세테이트에 취하고 메탄올(150 mL)로 침전시켰다. 침전을 여과로 회수하고 소량의 알리코트의 메탄올로 세척하고 수일간 고 진공하에 50 ℃에서 건조하였다. 최종 생성물을 무색의 분말 형태로 1.36 그램(75%)의 수율로 얻었다. DSC: 109.9 ℃의 T_g; TGA: 197.4 ℃의 T_d(5% 중량 손실); GPC(PMMA 표준에 대해): M_n = 3.82 kDa, M_w = 6.02 kDa, D = 1.57; ¹H-NMR (400 MHz, THF-d ₈ ) δ 8.25 - 8.09 (1.4%), 7.69 - 7.62 (8.5%), 7.57 - 7.25 (32.4%), 7.22 - 7.15 (2.3%), 7.12 - 6.98 (14.9%), 6.95 - 6.81 (6.0%), 5.41 - 5.28 (1.8%), 3.51 - 3.40 (1.8%), 1.70 - 1.01 (30.9%) [적분비 δ8.20/5.36 42:58]; ¹³C-NMR (101 MHz, THF-d ₈)) δ 156.75, 156.64, 156.46, 156.43, 154.81, 154.45, 139.18, 139.11, 137.34, 136.43, 135.94, 135.42, 134.05, 134.03, 133.39, 133.37, 133.33, 133.32, 131.73, 131.43, 129.97, 129.84, 129.71, 129.37, 128.56, 128.32, 127.89, 127.86, 127.13, 127.00, 118.81, 118.53, 118.48, 118.45, 117.57, 117.54, 117.49, 117.39, 117.23, 101.23, 101.22, 101.18, 101.10, 100.27, 84.37, 75.08, 67.57, 34.40, 33.25, 26.77, 25.01, 24.87, 21.72.
pBEBA-2,4-DBP-CHVE (60%). Under nitrogen, 2.0 g of polymer pBEBA-2,4-DBR-CHVE (100%, M _n = 3.94 kDa, M _w = 6.17 kDa, D = 1.56 kDa) was dissolved in THF (15 ml) and deuterated benzene (5 ml) ≪ / RTI > Trifluoroacetic acid (398 microliters, 267 milligrams, 2.34 millimoles) was added to water (2.81 milliliters) and THF (6.42 milliliters) to prepare a 0.54 M aqueous trifluoroacetic acid solution. 64.0 microliters of TFA / water / THF mixture was added to the reaction solution using a syringe. The reaction solution was maintained at 30 캜. During the reaction a single-scan NMR sample was taken and the acetal protons

And phenol protons

And the progress of the defibrillation was estimated. Once the integral ratio of acetal to phenol was 60:40, triethylamine (30 microliters) was added to quench the reaction. The solvent was removed by rotary evaporation. The resulting residue was taken up in a small amount of ethyl acetate and precipitated with methanol (150 mL). The precipitate was collected by filtration, washed with a small amount of an aliquot of methanol and dried at 50 캜 for several days under high vacuum. The final product was obtained in the form of a colorless powder in a yield of 1.36 grams (75%). DSC: T _g of 109.9 ℃; TGA: T _d (5% weight loss) at 197.4 캜; GPC (for the PMMA standard): M _n = 3.82 kDa, M _w = 6.02 kDa, D = 1.57; ¹ H-NMR (400 MHz, THF- d ₈ )? 8.25-8.09 (1.4%), 7.69-7.62 (8.5%), 7.57-7.25 (32.4%), 7.22-7.15 14.9%), 6.95-6.81 (6.0%), 5.41-5.28 (1.8%), 3.51-3.40 (1.8%) and 1.70-1.01 (30.9%) [total secretion δ8.20 / 5.36 42:58]; ¹³ C-NMR (101 MHz, d ₈ -d ₈ )? 156.75, 156.64, 156.46, 156.43, 154.81, 154.45, 139.18, 139.11, 137.34, 136.43, 135.94, 135.42, 134.05, 134.03, 133.39, 133.37, 133.33, 133.32 , 131.73, 131.43, 129.97, 129.84, 129.71, 129.37, 128.56, 128.32, 127.89, 127.86, 127.13, 127.00, 118.81, 118.53, 118.48, 118.45, 117.57, 117.54, 117.49, , 100.27, 84.37, 75.08, 67.57, 34.40, 33.25, 26.77, 25.01, 24.87, 21.72.

Production Example 10

pBEBA-2,4-DBP-CHVE (30%). A 30% CHVE-protected polymer was obtained following the procedure of the preceding example, except that the reaction was carried out up to 70% conversion as determined by NMR assays of acetal and phenol protons. If 30% deprotection is not achieved after several days of stirring, water is added at 0.05 equivalents to promote further deprotection.

1.00 grams of the colorless powder of the first representative batch (100%, M _n = 3.94 kDa, M _w = 6.17 kDa, D = 1.56) yielded from polymer pBEBA-2,4-DBR-CHVE: Yield: 602 mg (73% . DSC: T _g of 117.5 ℃; TGA: T _d (5% weight loss) at 198.2 ° C; GPC (for the PMMA standard): M _n = 3.86 kDa, M _w = 6.03 kDa, D = 1.63; ¹ H-NMR (400 MHz, THF- d ₈ )? 8.22-8.12 (2.2%), 7.73-7.59 (8.9%), 7.57-7.14 (37.6%), 7.12-6.76 (23.7% 1.1%), 3.51 - 3.39 (1.2%), 1.70 - 1.03 (25.4%), and [antigens δ 8.20 / 5.36 67:33].

3.30 g of a second representative batch (100%, M _n = 3.94 kDa, Mw = 6.17 kDa, D = 1.56) starting from the polymer pBEBA-2,4-DBR-CHVE: Yield 2.21 g (82%) of a colorless powder. DSC: T _g of 135.6 캜; TGA: 5% weight loss at 233.3 캜; GPC (for the PMMA standard): M _n = 4.53 kDa, M _w = 8.35 kDa, D = 1.84; ¹ H-NMR (400 MHz, THF- d ₈ )? 8.23-8.15 (2.6%), 7.72-7.58 (9.0%), 7.57-7.12 (39.6%), 7.12-6.77 (24.6% 1.1%), 3.49 - 3.37 (1.3%), 1.70 - 0.79 (22.04%), [antralia δ 8.20 / 5.36 70:30]; ¹³ C NMR (101 MHz, d6 -D8)? 156.46, 156.43,158.81,154.44,139.20,137.34,136.42,135.92,135.42,134.05,133.39,133.32,131.73,131.43,129.96,129.84,129.71,129.62,129.39, 129.36, 128.88, 128.55, 128.32, 127.89, 127.52, 127.12, 127.00, 118.80, 118.53, 118.48, 118.44, 117.57, 117.54, 117.49, 117.39, 117.22, 111.20, 101.27, 101.21, 101.15, 100.27, 84.38, 75.08, 34.40, 33.25, 26.76, 25.01, 24.87, 21.72.

Production Example 11

pBEBA-2,4-DBP-CHVE (30%). This example illustrates the synthesis of partially protected poly (aryl acetal) polymers using mixed polymerization using a phenol-soluble Suzuki coupling catalyst. Under nitrogen, 2,2'- ((phenylmethylene) bis (oxy)) bis (4,1-phenylene)) -bis (4,4,5,5-tetramethyl- (1.632 grams, 4.316 millimoles, 0.285 equivalents) was added to a rounded flask equipped with a stirrer, a condenser, a condenser, a condenser, a condenser, Bottom flask. Under nitrogen, in separate vials, potassium phosphate (10.06 grams, 47.4 mmol, 3.13 eq.) Was dissolved in oxygenated water (13 milliliters). Under nitrogen, Pd (crotyl) (P-tBu ₃ ) Cl (6.0 mg, 15 micromoles, 0.001 eq.) Was dissolved in degassed 1,4-dioxane (200 microliters) in a separate vial. 1,4-dioxane (50 milliliters) was added to the main reaction vessel, and potassium phosphate solution was added. The mixture was vigorously stirred until an emulsion was formed. Thereafter, the catalyst solution was added through the cannula. The reaction was stirred for 5 hours and then 2,4-dibromophenol (2.537 grams, 10.07 mmol, 0.665 eq.) Was added. The reaction solution was vigorously stirred overnight. After 20-22 hours, a phenylboronic acid end cap (0.277 grams, 2.27 mmol, 0.15 eq) was added. The reaction solution was vigorously stirred overnight. After 20-24 h, a bromobenzene end cap (477 microliters, 4.54 mmol, 0.30 eq) was added. The reaction solution was vigorously stirred overnight. 50 milliliters of diluted brine and 100 milliliters of ethyl acetate were added and the reaction solution was worked up by shaking in an extraction funnel. The aqueous layer was removed and the remaining organic phase was further washed with brine (1 x 50 mL). The organic phase was transferred to a round bottom flask equipped with a reflux condenser, a saturated aqueous solution of sodiumdiethyldithiocarbamate (~10 milliliters) was added, and the mixture was vigorously stirred under reflux for 60 minutes. The organic phase was separated, dried over magnesium sulfate and filtered through a three layer plug of CELITE ^TM diatomaceous earth (top ~ 0.25 inch), FLORISIL ^TM activated magnesium silicate (medium 0.15 inch) and silica gel (bottom 0.15 inch). The crude product was eluted well using 200 milliliters of ethyl acetate and the combined organic phases were washed with deionized water (5 x 50 milliliters) and concentrated on a rotary evaporator. The residue was taken up in ethyl acetate (~ 50 milliliters) using toluene (5-10 milliliters). The polymer was added dropwise to stirred methanol (700 milliliters). Once the addition was complete, the suspension was stirred for 30 minutes and then submersed. The precipitate was collected by filtration through a pre-washed disposable filter cartridge and air dried. The residue was taken up again with ethyl acetate (~ 50 milliliters) using toluene (5-10 milliliters) and the precipitation procedure was repeated twice. After the final precipitation, the filter cake was dried at ~ 65 ° C overnight in a high vacuum oven. The product was obtained in the form of a colorless powder (5.55 grams, 91% polymerization yield). DSC: T _g of 136.1 ℃; TGA: T _d (5% weight loss) at 270.9 캜; GPC (for PS standard): M _n = 6.44 kDa, M _w = 13.4 kDa, D = 2.08; ^{1 H NMR (500 MHz, THF-} d 8) δ 8.28 - 8.16 (2.8%), 7.75 - 7.62 (9.4%), 7.60 - 7.16 (40.0%), 7.13 - 6.80 (24.7%), 5.43 - 5.31 (1.1 %), 3.53 - 3.37 (1.2%), 1.71 - 1.06 (23.0%); [Integrity δ8.20 / 5.36 71:29]; ¹³ C NMR (101 MHz, THF-d8) δ 156.74, 156.44, 156.40, 154.83, 154.42, 139.16, 137.33, 136.41, 135.90, 135.40, 134.07, 134.04, 133.99, 133.36, 133.34, 133.32, 131.72, 131.42, 129.95, 129.82, 129.68, 129.61, 129.38, 129.36, 129.33, 128.54, 128.31, 127.88, 127.51, 127.10, 126.99, 118.79, 118.52, 118.49, 118.47, 118.44, 117.55, 117.52, 117.48, 117.38, 117.21, 101.20, 101.15, 101.03, 100.26, 84.37, 75.08, 67.57, 34.38, 33.23, 26.75, 24.85, 21.71.

Production Example 12

pBEBA-2,4-DBP (0%). Under nitrogen, 2,2'- ((phenylmethylene) bis (oxy)) bis (4,1-phenylene)) -bis (4,4,5,5-tetramethyl- (6.000 grams, 11.36 millimoles, 1.000 equivalents) and 2,4-dibromophenol (2.718 grams, 10.79 millimoles, 0.950 equivalents) were combined in a round bottom flask. Under nitrogen, in separate vials, potassium phosphate (7.54 grams, 35.5 millimoles, 3.13 equivalents) was dissolved in oxygenated water (10 milliliters). Under nitrogen, Pd (crotyl) (P-tBu ₃ ) Cl (4.5 milligrams, 11.4 micromoles, 0.001 eq.) Was dissolved in degassed 1,4-dioxane (200 microliters) in a separate vial. 1,4-dioxane (45 milliliters) was added to the main reaction vessel, followed by the addition of potassium phosphate solution. The mixture was vigorously stirred until a homogeneous emulsion was formed. Thereafter, the catalyst solution was added through the cannula. The reaction solution was vigorously stirred overnight. After 20-22 hours, a phenylboronic acid endcap (208 mg, 1.70 mmol, 0.15 eq) was added. The reaction was stirred for 7-8 hours and then bromobenzene end cap (358 microliters, 3.41 mmol, 0.30 eq) was added. The reaction solution was vigorously stirred overnight. 50 mL of diluted brine and 100 mL of ethyl acetate were added, followed by shaking in an extraction funnel to post-treat the reaction mixture. The aqueous layer was removed and the remaining organic phase was further washed with brine (1 x 50 mL). The organic phase was transferred to a round bottom flask equipped with a reflux condenser, a saturated aqueous solution of sodiumdiethyldithiocarbamate (~10 milliliters) was added, and the mixture was vigorously stirred under reflux for 60 minutes. Brine (30 milliliters) was added and the organic phase was separated and dried over magnesium sulphate and washed with three layers of CELITE ^TM diatomite (top ~ 0.25 inch), FLORISIL ^TM activated magnesium silicate (middle 0.15 inch) and silica gel Filtered through a plug. The crude product was eluted thoroughly with ethyl acetate (200 milliliters) and the combined organic phases were concentrated on a rotary evaporator. The residue was taken up in ethyl acetate (~ 50 milliliters) using toluene (5-10 milliliters). The polymer was added dropwise to stirred methanol (700 milliliters). Once the addition was complete, the suspension was stirred for 30 minutes and then submersed. The precipitate was collected by filtration through a pre-washed disposable filter cartridge and air dried. The residue was taken up again with ethyl acetate (~ 50 milliliters) using toluene (5-10 milliliters) and the precipitation procedure was repeated twice. After the final precipitation, the filter cake was dried at ~ 65 ° C overnight in a high vacuum oven. The product was obtained in the form of a colorless powder (3.68 g, 88% polymerization yield). DSC: T _g of 147.7 캜; TGA: T _d (5% weight loss) at 291.0 캜; GPC (for PS standard): M _n = 5.98 kDa, M _w = 13.5 kDa, D = 2.26; ¹ H NMR (400 MHz, THF- d ₈ )? 8.23 - 8.16 (4.8%), 7.73 - 7.17 (61.7%), 7.09 - 6.98 (22.7%), 6.93 - 6.75 (11.3%); ^{13 C NMR (101 MHz, THF-} d 8) δ 156.46, 154.81, 139.19, 136.41, 134.06, 134.04, 133.41, 133.38, 131.43, 130.32, 129.95, 129.70, 129.62, 129.39, 129.37, 129.34, 128.88, 128.32, 127.88 , 127.52, 127.13, 118.48, 118.44, 118.27, 117.57, 117.54, 117.40, 101.27, 101.15, 101.08, 101.03, 67.57.

Polymer shredding and deprotection

For polymer degradation experiments, a 4.5 kDa sample (20 mg) of pBEBA-2,4-DBP-CHVE whose synthesis was described in Preparative Example 8 was dissolved in 827 microliters of deuterated-THF. The NMR spectrometer was equilibrated to 30 < 0 > C and a single pulse NMR spectrum was taken to adjust the receiver gain. 27 microliters of 0.11 M triflic acid aqueous solution was added to initiate the reaction. A single pulse NMR spectrum was repeated every 30 seconds for the first 2.5 minutes and then the time interval was increased for at least 8 hours. Arrayed integrals were performed using MestReNova (version 8.0.2-11021, 2012 Mestrelab research SLC) after phase adjustment and baseline correction.

Figure 1 shows the polymer backbone and side chain breakdown of the polymer pBEBA-2,4-DBP-CHVE obtained in Preparative Example 8 after treatment with dilute aqueous triflic acid. By deprotection of one equivalent of ethyl vinyl ether, one equivalent of acetaldehyde is formed which can be monitored by the integration of the diagnostic aldehyde proton through ¹ H-NMR (top curve). Skeletal decomposition results in one equivalent of benzaldehyde formation per degraded acetal unit, which can be monitored by integration of the diagnostic benzaldehyde proton through ¹ H-NMR (bottom curve). Skeleton and side chain decomposition are two independent processes that occur at different rates. The acid sensitivity of the skeletal acetals and the side chain acetals can be independently controlled by selecting suitable substitution patterns on each acetal.

Figure 2 shows that acid treatment significantly affects the solubility characteristics of the polymer systems disclosed herein when pBEBA-2,4-DBP-CHVE (Preparative Example 8) is used as the example substrate.

In vial 1, 5 milligrams of untreated pBEBA-2,4-DBP-CHVE (4.8 kDa) was dissolved in 200 microliters of propylene glycol monomethyl ether acetate (PGMEA). A few minutes later, a clear solution of pBEBA-2,4-DBP-CHVE in PGMEA was formed, demonstrating the solubility in solvents commonly used in photoresist applications.

In vial 2, 2.5 milligrams of untreated pBEBA-2,4-DBP-CHVE (4.8 kDa) was dissolved in 100 microliters of tetrahydrofuran (THF).

In vial 3, 2.5 milligrams of pBEBA-2,4-DBP-CHVE (4.8 kDa) was dissolved in 100 microliters of THF. When the vial was further treated with about 50 microliters of concentrated trifluoroacetic acid, the contents of the vial turned red.

In vial 4, when 50 microliters of the untreated storage solution from vial 2 was added to 300 microliters of 0.26 N TMAH aqueous solution, a thick precipitate of insoluble polymer was formed. This shows that the untreated pBEBA-2,4-DBP-CHVE is insoluble in aqueous tetramethylammonium hydroxide (TMAH) solution (THF is miscible with 0.26 N TMAH aqueous solution).

In vial 5, 50 microliters of acid-treated polymer solution from vial 3 is added to 0.26 N aqueous TMAH solution to give a clear orange colored solution, which is acid-treated (and shredded) pBEBA- 2,4-DBP-CHVE is soluble in aqueous TMAH solution.

The precipitate of the vial (4) was isolated by filtration and analyzed by NMR to show that the precipitate was an intact pBEBA-2,4-DBP-CHVE polymer (a). Analysis of the contents of the vial 5 by liquid chromatography-mass spectrometry (LC-MS) indicated that the three primary compounds by the integral were [1,1 ': 3', 1 "-terphenyl] -4,4 ' , 4 "-triol (a), benzaldehyde (b) (identified by NMR but not in mass spectrometry), and [1,1 ': 3', 1" 4 ', 5' -bis (4-hydroxyphenyl) - [1,1 ': 2', 1 ": 2 ", 1" '-tetraphenyl] -4,4' , 4 "', 5" -tetraol (c). Integration of the compounds (a), (b) and (c) together on an LC curve at 250 nm was measured to be> 96% of the total integral of the LC curve.

Claims (10)

A polymer comprising a plurality of repeating units having the structure:

or

In the above formula
R ¹ and R ² in each occurrence are independently hydrogen, unsubstituted or substituted C _1-18 linear or branched alkyl, unsubstituted or substituted C _3-18 cycloalkyl, unsubstituted or substituted C _6-18 aryl , Or unsubstituted or substituted C _3-18 heteroaryl; R ¹ and R ² are optionally covalently linked to each other to form a ring comprising -R ¹ -CR ² -; In each case Ar ¹ , Ar ² , and Ar ³ independently represent unsubstituted or substituted C _6-18 arylene, or unsubstituted or substituted C _3-18 heteroarylene; With the proviso that at least one of Ar ¹ , Ar ² and Ar ³ is substituted by at least one functional group selected from hydroxyl, acetal, ketal, ester and lactone. The polymer of claim 1, wherein, in at least one repeat unit, at least one of Ar ¹ , Ar ² and Ar ³ is substituted by at least one hydroxyl. The polymer of claim 1, wherein Ar ¹ , Ar ² and Ar ³ in each case are independently 1,3-phenylene or 1,4-phenylene. Any one of claims 1 to A method according to any one of claim 3, wherein the Ar ¹ and ^{Ar 2 -Ar 1 -OCO-Ar 2} - polymer Ignored connected covalently to each other to form a ring structure containing. 5. A compound according to any one of claims 1 to 4, wherein R < ¹ > is hydrogen in each case; In each case R < ^{2 >} is unsubstituted or substituted phenyl. The method according to claim 1,

Substructure within

Is selected from the group consisting of:

7. The method according to any one of claims 1 to 6,

Substructure within

Is selected from the group consisting of:

The polymer according to claim 1, comprising a plurality of repeating units selected from the group consisting of:

(Wherein R ¹⁰¹ is hydrogen or hydroxyl, R ¹⁰² is a hydroxyl or when R ¹⁰¹ is hydrogen, R ¹⁰² is R ¹⁰¹ is a hydroxyl silil when a hydrogen);

Wherein R ²⁰¹ is hydrogen or -OCHVE, R ²⁰² is hydrogen when R ²⁰¹ is hydrogen, or when R ²⁰¹ is -OCHVE, wherein -OCHVE is

to be);

Wherein R ³⁰¹ is -OC (═O) -CH ₃ or -OCHVE, R ³⁰² is -OCHVE when R ³⁰¹ is -OC (═O) -CH ₃ , or -OCHVE when R ³⁰¹ is -OCHVE (= O) a -CH _3);

(Wherein R ⁴⁰¹ is a hydroxyl or -OCHVE, R ⁴⁰² or R ⁴⁰¹ is a hydroxyl -OCHVE when silil, R ⁴⁰¹ is a hydroxyl -OCHVE when);

Wherein R ⁵⁰¹ is hydrogen or hydroxyl, R ⁵⁰² is hydroxyl when R ⁵⁰¹ is hydrogen, or R ⁵⁰² is hydrogen when R ⁵⁰¹ is hydroxyl;

(Wherein R ⁶⁰¹ is hydrogen or -OCHVE, R ⁶⁰² is -OCHVE when R ⁶⁰¹ is hydrogen, or hydrogen when R ⁶⁰¹ is -OCHVE);

Wherein R ⁷⁰¹ is hydrogen or hydroxyl, R ⁷⁰² is hydroxyl when R ⁷⁰¹ is hydrogen, or R ⁷⁰² is hydrogen when R ⁷⁰¹ is hydroxyl;

(Wherein R ⁸⁰¹ is hydrogen or -OCHVE, R ⁸⁰² is -OCHVE when R ⁸⁰¹ is hydrogen, or hydrogen when R ⁸⁰¹ is -OCHVE);

Wherein R ⁹⁰¹ is hydrogen or hydroxyl, R ⁹⁰² is hydroxyl when R ⁹⁰¹ is hydrogen, or R ⁹⁰² is hydrogen when R ⁹⁰¹ is hydroxyl;

(Wherein R ¹⁰⁰¹ is hydrogen or -OCHVE, R ¹⁰⁰² is hydrogen when R ¹⁰⁰¹ is hydrogen, or R ¹⁰⁰¹ is -OCHVE);

;

Wherein R ¹¹⁰¹ is hydrogen or -O-CH ₂ -C (= O) -O-Ad and R ¹¹⁰² is -O-CH ₂ -C (= O) -O-Ad when R ¹¹⁰¹ is hydrogen , R ¹¹⁰¹ is _{-O-CH 2 -C (= O} ) -O-Ad is hydrogen when, where _{-O-CH 2 -C (= O} ) -O-Ad is

;

;

;

;

;

;
And combinations thereof). 2. A compound according to claim 1, wherein Ar < ¹ > and Ar < ² > Ar ³ is an alkylene unsubstituted or substituted 1,3-phenylene in each case, where Ar ³ in at least 40 mole percent of the plurality of repeating units is substituted by at least one hydroxyl; In each case R ¹ is hydrogen; In each case R < ² > is phenyl. 10. An article comprising a polymer of any one of claims 1 to 9.

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